改性生物炭催化过硫酸氢钾降解染料废水中罗丹明6G的研究
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摘要
通过煅烧-浸渍法制备了铁酸锰和钴共改性生物碳(Co/MnFe_2O_4/Biochar,CMB),采用扫描电镜(SEM)、X射线能谱仪(EDS)、X射线衍射仪(XRD)、傅里叶红外光谱仪(FTIR)和N_2吸脱附等温仪(BET)对CMB进行形貌观察和结构表征,并用其催化过硫酸氢钾(PMS)降解染料罗丹明6G(Rh 6G),研究了CMB投加量、PMS投加量、溶液初始pH值、水中常见物质(如Cl~-、HCO_3~-、H_2PO_4~-、HA)对CMB/PMS体系降解Rh 6G的影响。实验结果表明,随着CMB和PMS投加量的增大,Rh 6G降解效率也随之增高。在溶液初始pH在5-9范围内,Rh 6G的降解率可达98%以上。Cl~-、HCO_3~-、H_2PO_4~-、HA对CMB催化PMS降解Rh 6G影响微弱。自由基猝灭反应实验结果证明SO_4·~-、~1O_2和O_2~-·对Rh 6G的降解起主要作用。重复利用实验表明,CMB经过五次循环使用后,降解率仍可达76.7%。
Modified biochar(Co/MnFe_2O_4/Biochar,CMB)was prepared by calcination impregnation-process.The morphology and structure of CMB were characterized by SEM,EDS,XRD,FTIR and BET.CMB was used to activate peroxymonosulfate(PMS)to degrade Rhodamine 6G(Rh 6G).The effects of CMB dosage,PMS dosage,solution initial pH,common ions of waterbody(for example:Cl~-、HCO_3~-、H_2PO_4~-、HA)on the degradation of Rh 6G were studied.Experimental results showed that the greater the dosage of CMB or PMS,the better the degradation efficiency.The degradation rate of Rh 6G could reach more than 98% in the solution initial pH range of 5-9.Cl~-,HCO_3~-,H_2PO_4~-,HA had little effect on the degradation of Rh 6G.The results of free radical quenching experiments indicated that SO_4~-·,~1O_2 and O_2~-·played a major role in the degradation of Rh 6G.Reuse experiments showed that after five cycles of CMB,the degradation rate could still reach 76.7%.
Modified biochar(Co/MnFe_2O_4/Biochar,CMB)was prepared by calcination impregnation-process.The morphology and structure of CMB were characterized by SEM,EDS,XRD,FTIR and BET.CMB was used to activate peroxymonosulfate(PMS)to degrade Rhodamine 6G(Rh 6G).The effects of CMB dosage,PMS dosage,solution initial pH,common ions of waterbody(for example:Cl~-、HCO_3~-、H_2PO_4~-、HA)on the degradation of Rh 6G were studied.Experimental results showed that the greater the dosage of CMB or PMS,the better the degradation efficiency.The degradation rate of Rh 6G could reach more than 98% in the solution initial pH range of 5-9.Cl~-,HCO_3~-,H_2PO_4~-,HA had little effect on the degradation of Rh 6G.The results of free radical quenching experiments indicated that SO_4~-·,~1O_2 and O_2~-·played a major role in the degradation of Rh 6G.Reuse experiments showed that after five cycles of CMB,the degradation rate could still reach 76.7%.
引文
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[3]F.Chen,Q.Yang,Y.L.Wang,et al.Novel ternary heterojunction photocatalyst of Ag nanoparticles and gC3N4 nanosheets co-modified BiVO4 for wider spectrum visible-light photocatalytic degradation of refractory pollutant[J].Appl Catal:B,2017,205:133-147.
[4]Ji Fei,Li Caolin,Wei Xiyu,et al.Efficient performance of porous Fe2O3 in heterogeneous activation of peroxymonosulfate for decolorization of Rhodamine B[J].Chem Engine J,2013,231:434-440.
[5]Ji Fei,Li Caolin,Liu Yi,et al.Heterogeneous activation of peroxymonosulfate by Cu/ZSM5 for decolorization of Rhodamine B[J].Separa Purific Technol,2014,135:1-6.
[6]Anipsitakis G P,Dionysiou D D.Radical generation by the interaction of transition metals with common oxidants[J].Environm Sci Technol,2004,38(13):3705-3712.
[7]Chen X,Chen J,Qiao X,et al.Performance of nano-Co3O4/peroxymonosulfate system:Kinetics and mechanism study using Acid Orange 7 as a model compound[J].Appl Cataly B Environm,2008,80(1):116-121.
[8]Liang H,Sun H,Patel A,et al.Excellent performance of mesoporous Co3O4/MnO2,nanoparticles in heterogeneous activation of peroxymonosulfate for phenol degradation in aqueous solutions[J].Appl Cataly B Environm,2012,127(1):330-335.
[9]Shi P,Su R,Wan F,et al.Co3O4,nanocrystals on graphene oxide as a synergistic catalyst for degradation of Orange II in water by advanced oxidation technology based on sulfate radicals[J].Appl Cataly B Environm,2012,123-124(12):265-272.
[10]Hu P,Long M.Cobalt-catalyzed sulfate radical-based advanced oxidation:A review on heterogeneous catalysts and applications[J].Appl Cataly B Environm,2016,181:103-117.
[11]Chen L,Cai T,Sun W,et al.Mesoporous bouquet-like Co3O4 nanostructure for the effective heterogeneous activation of peroxymonosulfate[J].J Taiwan Instit Chem Engin,2017,80:720-727.
[12]Yao Y,Cai Y,Lu F,et al.Magnetic recoverable MnFe□O□ and MnFe□O□-graphene hybrid as heterogeneous catalysts of peroxymonosulfate activation for efficient degradation of aqueous organic pollutants[J].J Hazard Mater,2014,270(3):61-70.
[13]Deng J,Feng S F,Ma X,et al.Heterogeneous degradation of Orange II with peroxymonosulfate activated by ordered mesoporous MnFe2O4[J].Separa Purific Technol,,2016,167:181-189.
[14]Zhang T,Zhu H,Croué J P.Production of sulfate radical from peroxymonosulfate induced by a magnetically separable CuFe2O4 spinel in water:efficiency,stability,and mechanism[J].Environm Sci Technol,2013,47(6):2784-2791.
[15]F.Ghanbari,M.Moradi.Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants:review[J].Chem Engine J,2017,310:462-469.
[16]Rani S K,Easwaramoorthy D,Bilal I M,et al.Studies on Mn(II)-catalyzed oxidation of α-amino acids by peroxomonosulphate in alkaline medium-deamination and decarboxylation:A kinetic approach[J].Appl Cataly A Gene,2009,369(1):1-7.
[17]Anipsitakis G P,Dionysiou D D.Degradation of organic contaminants in water with sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt[J].Environm Sci Technol,2003,37(20):4790-4797.
[18]Liang P,Zhang C,Duan X,et al.An insight into metal organic framework derived N-doped graphene for the oxidative degradation of persistent contaminants:formation mechanism and generation of singlet oxygen from peroxymonosulfate[J].Environm Sci Nano,2017,4:315-324.
[19]Qi C,Liu X,Ma J,et al.Activation of peroxymonosulfate by base:Implications for the degradation of organic pollutants[J].Chemosph,2016,151:280-288.
[20]Feraru S,Borhan A I,Samoila P,et al.Development of visible-light-driven Ca2Fe1-xSmxBiO6 double perovskites for decomposition of Rhodamine 6G dye[J].J Photochem Photobiol A:Chem,2015,307-308:1-8.